Ethylene-bridged dibenzanthrone compounds and process for their preparation



Patented May 5, 1953 ETHYLENE-BRIDGED DIBEN'ZANTDIY'IRONE COMPOUNDS AND PROCESS FOR THEIR PREPARATION James M. Straley, Kingsport, Tenn., assignor to I Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Original application April 4, 1950,

Serial No. 153,996. Divided and this application June 1, 1951, Serial No. 229,543

This invention relates to a process for preparing condensation products of the benzanthrone series and to certain of the benzanthrone compounds as new compounds.

In accordance with the process of my invention a IO-methyleneanthrone compound which is unsubstituted in at least one of the 4- and 5- positions is condensed with LB-cyclohexadiene to obtain new valuable vat dye intermediates which are probably Bz 2, Bz 2'-ethylene-bridged dibenzanthronyl compounds. These latter compounds are fused by means of KOH or NaOH to form new vat dye compounds which in turn are oxidized to form the'final vat dye products of my new process.

IO-methyleneanthrone has the probable formula:

H CH2 The numbering given is that employed herein.

It is an object of my invention to provide new valuable vat dye intermediates which are probably Bz 2, B2 2-ethylene-bridged dibenzanthronyl compounds. Another object is to provide new valuable vat dyes which are probably dibenzanthrone compounds in which the 16- and 17-p0sitions are bridge by an ethylene linkage. A further object is to provide valuable vat dyes which are probably dibenzanthrone compounds in which and l7-positions are bridged by a j the 16- --CI-I=CI-I- linkage. Another object is to provide a satisfactory process for the preparation of the compounds of the invention.

In carrying out the process of the invention a IO-methyleneanthrone compound which is punsubstituted in at least one of the 4- and 5-positions is condensed with 1,3-cyclohexadiene in the presenceof a mild oxidizing agent such as xygen and nitrohydrocarbons and their derivaives. A number of the nitrohydrocarbon type of oxidizing agents are disclosed hereinafter. Nitroalkanes, aqueous solutions of nitrobenzene sulfonic acids and aromatic nitrocompounds differ only in degree and not in kind of influence. Although nitroalkanes such as nitromethane, nitroethan, n-nitropropane (CHsCHzC'HzNOz) and n-nitrobutane (CH3CH2CH2CH2NO2), for example, and although 'nitrobenzene sulfonic acids such aso-nitrobenzene sulfonic acid-,- m-nitro- 3 Claims. (Cl. 260-353) benzene sulfonic acid ionic acid, for example, can be used, I prefer to employ aromatic nitrohydrocarbons such as nitrobenzene, o-nitrotoluene, m-nitrotoluene, p-nia -trotoluene, a nitro xylene such as 2-nitro-1,3-dimethylbenzene, 4 nitro 1,2-dimethylbenzene,

etc.; a-nitronaphthalene, p-nitronaphthalene and a-nitromethylnaphthalene, for example.

The use of a strong oxidizing agent, such as .potassium' permanganate, nitric acidor potas sium dichromate, for example, should be avoided in this phase of my invention. If strong oxidizing agents were used, particularly at high temperatures, side reactions would occur, due to' either the ease of oxidizing methyleneanthrone compounds to anthraquinone compounds or possible destruction of the desired reaction product, thereby seriously lowering the yield.

The reaction temperature does not appear to be critical as the products can be obtained at ordinary temperatures as well' as at high temperatures, "Temperatures of from about 25 C. to

about 200 C., for example, can be employed. Temperatures of from about C. to about C. appear most suitable and are preferred. Where low temperatures are employed, a longer reaction time is required Temperatures in excess of 200 C. appear to reduce the yield and to cause contamination, apparently by polymerization of the methyleneanthrone competing with the desired addition reaction.

The reaction, as illustrated with reference to lO-methyleneanthrone, is believed to proceed as followsz' 1 C O H and p-nitrobenzene sul- IO-methyleneanthrone compounds that can be employed include, for example, IO-methyleneanthrone, 10 methylene 2 chloroanthrone, 10- methylene-l-methylanthrone; 10-methylene.-4.--- bromoanthrone, IO-methylene-I-flixoroanthrone; lO-methylene-3-methylanthrone, IO-methylene- 3 -chloroanthrone, 10 methylene-2-methylan--- throne and IO-methylene-lechloroanthrone...

As previously indicated, by thaactionjofiicaustic... alkali such as KOH or NaOH'uponithe new vat" dye intermediates of the invention, new vat dye compounds are obtained. This 'reaction,-.as illus+ trated with reference to the unsubstituted-vat? dye intermediate is believed to take place as follows:

n The '2-..and 2 positions zoi the startinzwompound;

The new vat dye compound thus obtained dye cotton well from a hot, strongly alkaline vat. The dyeings obtained are attractive shades of blue and possess excellent wash-fastness. However, as explainedhereinaiter, these :new vat dye compounds which will be referred to herein as intermediate vat dye compounds are readily convertedto more. permanent dyestuffs, i. e., the finallproduct'sof'the present invention,

Thefinaliproducts of the invention are ob tained by oxidizing the intermediate vat dye comnoundsj'whichiin their" unsubstituted form have the: formula-IV; The oxidation can be carried out in a number of Ways. Thus oxidation can be eifctedxby heating the intermediate vat dye in air attemperaturesi above 160 C. either en masse or on the. fiber. The final products can also be obtained-by incorporating an oxidizin agent into the caustic alkali melts used in the formation of-"the intexmediaterzvat dyeicompomrdsiorctheiimtermediateivatz dye compoumis can'tbie oxidized to thefinali'vat dye products-by means of chemical i oxidizing agents. Further-,1exposureto'strong ultraviolet light; such-as that used in-a-pparatus for-testing the-light fastnessof dyeings, will also effect the transformationof the intermediate-vat dyecompounds' to the'fin'al products:

Thenonversion. of the new intermediate vat'dye' compounds to the. final vat" dye compounds is illustrated by .theiollowingequation" wherein arr. unsubstituted intermediate .vat. dye compound is employed .asihEstartihg .c'ompound;

must be unsubstituted. By the use of a compound which is substituted, for example, with a chlorine atom, a bromine atom, a fluorine. atom or a methyl group substituted vat dye compounds are obtained. The positions of the substituentor. substituents in the .vat"dye obtained are deter mined by the positiononpositlons occupied by. the substituent or substitixents in the starting compound.

The new vat dye compounds whichgin their unsubstituted form..have...the probable formula IV are easily obtained by introducing the new intermediates which imtheir unsubstituted form have the probable formula III into melts of KOH or NaOH at temperatures of from about 105 C. to about 160 6.." While a'ny'of the standard conditions: of. caustic ,fusions used in the vat dye industry appear to. be,suitable, the use of ethyl or methyl alcohol'potassium hydroxide'melts at temperatures of about 130 C. to about 155 C. appears advantageous and is preferred.

to besclarlyz understood that the .finalt.

products..-may. contain .snbstituentsf-and it, is here theprooessof our invention is carriedioutp Parts f are expressedas .part's' by, weight.

Pnmwuarmnrouzfliia:Dicflnmamznmras:

ExampZ-ed solution 0t.- 20.'6-.-. parts of Ill-methylenea-n: throne.and. 41"pa1TrtS of. 1,3eyeloheX-adiene. in: 1.10. parts ofl nitrcbenzene wereshaken. at roomtemq 10,;perature torsthree. weeks.-- The "reactiommixturo was? thenzrfilteredand. the solid: collected; on. the filter. WEJSQWEShGdTW-ithl ethyl alcoholz t-bright. yellow sol-id meltinggaboveifi 60*"0. wasaobtained.

Microscopicrexaminatiorr. discloses that the -prod.-

It probably has theformula numbered II. The yield of product was about 20% Example 2 Example 3 40 parts a .IO-methyleneanthrone in 200 parts of nitrobenzene were heated to 180 C. 12 parts of 1,3-cyclohexadiene in 20 parts of nitrobenzene 6. then filtered to recover the desired reaction product. The product obtained is a yellow powder dissolving in concentrated sulfuric acid with a red color.

Example 7 i 20 parts of a -methylenemethylanthrone (probably IO-methylene-l-methylanthrone) prepared from 1-methyl-9-anthrone were reacted with 5 parts of 1,3-cyclohexadiene exactly in acwere gradually added over a period of 30 minutes,

with stirring at a temperature of 185 C.-190- C. The temperature was maintained at 180 C.-190 C. for 3.5 hours longer, after which 4 parts of 1,3- cyclohexadiene were added and the reaction mixture refluxed for 1 hour. The reaction mixture was then cooled to 80 C., diluted with an equal volume of ethyl alcohol (methyl alcohol can also be used) allowed to cool to room temperature and then filtered. A heavy crop of bright yellow crystals having the same properties and formula as the product of Example 1 was obtained. The yield of product was about 68%. A solution of the product in concentrated sulfuric acid hasa bluish-red color.

Example 4 '22 parts of a 10-methylene-dichloroanthrone prepared from 1,4-dichloroanthrone (Ber. 62, 1971 (1929)) were heated and stirred at1'l0 C.- 180. C. with 5 parts of 1,3-cyclohexadiene in 80 parts of o-nitrotoluene for 6 hours. The reaction mixture was then cooled to 80 C., diluted with an equal volume of ethyl alcohol (methyl alcohol can also be used), allowed to cool to room temperature and then filtered. The product obtained is a brown amorphous material subliming with some decomposition at about 360 C.

Example 6 parts of a 10-methylenechloroanthrone (probably 10-methylene-1-chloroanthrone) ,-prepared from 1-chloro-9-anthrone (J. CS. 123, 2553), in 100 parts of nitrobenzene were heated to 180 C. 6 parts of 1,3-cyclohexadiene in 10 parts ofnitrobenzene were gradually added over a period of 30 minutes with stirring at'a temperature of 185 C.-190 C. The temperature was maintained at 180 C.-190 C. for 3.5 hourslonger, after which 4 parts of 1,3-cyclohexadieneywere added and the reaction mixture refluxed for 1 hour. The reaction mixture was then cooled to 80 C., diluted with an equal volume" of ethyl alcohol, allowed to cool toroom temperature and cordance with the procedure described in Example 4. A brown product was obtained.

PREPARATION or INTERMEDIATE VAT Dras Example 8 parts of the condensation product of 10- methyleneanthrone and 1,3-cyclohexadiene obtained as in Examples 1, 2 or 3 were gradually added overaperiod of about 20 minutes at C.- C. to a smooth melt prepared from 500 parts of fiakepotassium hydroxide and 500 parts ofethyl alcohol. The temperature was allowed to rise to C. in about 30 minutes by distillation of the alcohol. The temperature was held at 140 C.- C. for 2 hours after which the reaction mixture was drowned in water and air-blown at 95 C. to isolate the dyestuff. About 90-95 parts of a blue powder, dissolving in concentrated sulfuric acid with a. cherry-red color and a slight blue-red fluorescence, were obtained. With alkaline hydrosulfite it forms a reddish-violet vat and cotton dyed therein is colored a pleasing blue after air-oxidation and soaping.

Example 9 100 parts of the product of Example 7 were treated exactly in accordance with the procedure described in Example 8. The product obtained is a blue powder which dyes cotton from an alkaline hydrosulfite vat blue shades which are slightly duller than those obtained with the dye product of Example 8.

Example 10 20 parts of the product of Example 5 were heated in a melt of 100 parts of KOH and 100 parts of ethyl alcohol at 125 C.-135 C. for 3.5 hours. The melt was then drowned in water and the dyestuff formed by the reaction was isolated by air-blowing and filtering. It dyes cotton greenish-blue shades from an alkaline hydrosulfite vat. From the behavior of the dyeings toward acid and alkali, it is believed that at least some of the chlorine-atoms initially present in the product of Example 5 have been replaced by hydroxyl groups. This replacement is believed to take place during. the fusion operation of this example.

PREPARATION or FINAL PRODUCTS Example 11 1'7 parts of the condensation product obtained as described in Example 3 were added at 130 C.- 135 C. to a melt prepared from parts of potassium hydroxide and 150 parts of ethyl al.- cohol. The reaction mixture was then heated to 150 C. and 20 parts of sodium nitrite were added. The temperature ros sharply and after the reaction had subsided, the reaction mixture was drowned in water, blown with air and filtered. 15.5 parts of a reddish-brown powder, dissolving to a violet solution in concentrated sulfuric acid jwithout fluorescence was obtained. -It dyes cotton from a blue vat a rather dull red or reddishbordeaux color which is very fast, especially with respect to light.

clEmamplea-rz 1'7 parts of thecondensation productobtained as described in"Example"'3 'weretreated exactly as described in Example 11 except that 20'parts of potassium chlorate were used in place of sodium nitrite. :Thesamedyestuff was obtained.

..Emample 13 1 1'7 parts of' the"condensation-product obtained as described in Example '3 were addedat 130 C- 135 C. to a meIt prepared'ffrom .150 parts'of potassium hydroxideandliio.parts of ethyl alcohol. The reaction mixture was then heated to 150 C.l55 C. andmaintained at this temperature, while stirring, -f.or.2 hours. Following this, the reaction-mixture was .drowned in water, blown with. air andifilteredto obtain-a blue vat dyestufi which-wassuspended in about 50 parts of water. 30 parts of sodium hypochloritesolution (about 5% active chlorine) were added to the dye. suspension and the reaction mixture was brought to 90 .C.95" C. and maintained at this temperature for'S to thourswith good stirring. The bright reddish-brown :d-yestufi formed was recoveredby filtration, washed with-water and dried. A yield of 14.9 .parts of apparentlythe identical product of Examples-ll andilz was obtained.

'The -reaction: can. be :carried out equally .well using a :mixtureof sodium chlorate and :hydrochloric. acidin place of sodium hypochloride.

ExampleI A sample of the blue dye'stuif obtained as described in Example 19 was finely= ground and heated in the air fGrB' tOIi1O.hOl1l'S at' 190 C.- 200 C. Thecolor changed".slowlynxto :areddish=brown. The product' 'obtaine'dzdyes' icotton from a blue-vat a reddish+bordeaux.colorzwhich is very fast, especially with respect i130 .light.

Example A swatch of cotton fabric dyed with the prodnot of Example S'Was placedin a Fadeometer and exposed until the 'colorjof the" fabric changed to that obtained by dyeing acotton'fabric from a vat with the dyestuii of Example 13. This requires 10 to 24 hoursdepending uponthe'concentration of the dyeing. The reddish dyeing so'produced matches in light-fastness'the dyeings obtainedwith'thedyestuif of Example '13.

...Eramlile .51 6

10 parts of the 'dyestuif obtained as described in Example 13 were dissolved .,in200 parts of chlorosulionic acid at 2O C. 5 parts .of bromine and 0.03 parts of sulfur were added and the reaction mixture was stirred for 16 hours at 25 C. C. The colorchanged from violet to red-brown. Thereactionfmixturewas then dilutedwith .200 parts of concentratedHzsol (sp. gr. 1.83) and poured ontoice. .The precipitated reaction product which isa vat dyestuif containing bromine -.was recovered byfiltration, washed with water and made into a paste. The vat of the'product was slightlyv greener andthe final dyeing on'cotton much "redder than that of the starting material.

3 Example 17 50 parts of the"dyestufiobtained asdescribed in'Example l3'were finely ground and'suspended in 300 parts 'of nitrobenzene at 50 C. -.'40"parts of nitric acid (sp. gr. 1.49) wereaddediand'ithe nc'action mixture was stirredoiorgseveralrihours at 60 C.- C. Then thereactionmixture-was poured into alkaline water and the nitrobenzene was removed by steam'distillation. The reaction mixture wasthenfiltered and .the reaction product. recovered on the filter washed with water and dried. A yield of '52 parts of a nitrated vat dye'stufi was obtained in the form of a dark powder. It vat dyed cotton .2. rather dull violet. The .light-fastness of the dyeings obtained on cottomwas excellent.

Example; 1 8

20 parts of the productobtained as described in Example 14 were refluxedand stirred under an elficient condenser-with *20'zpartsxof..bromine, 500 parts .of trichlorobenzene and 0.1"part: or iodinefor-A hours. The reaction :miXture was cooled, filtered, and the product recovered xon the'filter was washed with benzene. 1A yieldz'ot iii-parts of a bromine containing vat -.dyest1ifl which gives .a .much bluer :solutioninpconcentrated H2SO4 (sp.:gr. 1.83) and. a'redderzdyeing on cotton than does the starting material was obtained.

Dyeing with the 'vat dye compounds of the invention is performed according to the .usual strong-alkali'vat procedure. .Dyeing can be carried out as follows:

0.05 gramof dyestufi'are well ground-with'a few drops of Monopol oil (sulfonated zcastoroil) and rinsed into :a dye=bath. .The dye-bath is brought to a total volume of,.100 cc.,;using soft water, and 0.5-1 gramof NaOH and 0.75-1 gram of sodium hydrosulfite are added. The temperature of'the dye-=bath is raised to"-50 C. and 5grams ofa'wellwet-out cotton-goods'are entered and dyed' at' 50 'C.55"'C. for' 1 hour. The dyed cloth :is'removed, rinsed and *hung in air until-oxidation'is'complete. The dyeings are finished;by:a"20 minute boil in a 0.5% aqueous sodium carbonate solution-rinsing with water and drying.

While the manner'in which'my new vat'dye compounds are-applied to cotton, for example, constitutes no part of my invention, it will be understood that the dyeing procedure given above is merely illustrative and not limitative of the manner in which they maybe .appliedto cotton goods.

While 'methyleneanthrone and .a number .of substituted methyleneanthrone compounds are known compounds, itis here notedthat-m'ethyleneanthrone :can be prepared as described by K. H. Meyer, Liebigs Annalemvol. 420, pagel35 (.1920). Substituted .methyleneanthrone .compounds can be preparedby the method just referredxto for the preparationof methyleneanthrone :by the use of .azzsubstituted anthrone compound in place of anthrone.

This application -is..a..division of my copendingapplicationfierial. No...153,996, filed April 4. 1950.

Ifclaim:

1. The compounds having the'formula:

wherein :X- represents; a member .selected from the: group consisting. of a;hydrcgen atom; a chlorinezatom, .1 a bromine l atom, a 5 fluorine. atom and ai'methylzgronpr and" n rrepresentsya. small-whole number selected from the group consisting of 1 and 2.

2. The compounds having the formula:

H2O CH2 wherein X represents a chlorine atom and n is 2.

3. The compound which has the formula:

JAMES M- STRALEY. 2O

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date Kranzlein et a1 Nov. 19, 1929 Luttringhaus et a1. Feb. 28, 1933 Wvertz Ma 16, 1933 Scheyer Oct. 23, 1934 Schlichting et a1. May 5, 1942 

1. THE COMPOUND HAVING THE FORMULA: 